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Standard enthalpy of formation

In chemistry and thermodynamics, the standard enthalpy of formation or standard heat of formation of a compound is the change of enthalpy during the formation of 1 mole of the substance from its constituent elements in their reference state, with all substances in their standard states. The standard pressure value p = 105 Pa (= 100 kPa = 1 bar) is recommended by IUPAC, although prior to 1982 the value 1.00 atm (101.325 kPa) was used.[1] There is no standard temperature. Its symbol is ΔfH. The superscript Plimsoll on this symbol indicates that the process has occurred under standard conditions at the specified temperature (usually 25 °C or 298.15 K). Standard states are as follows:

  • For a gas: the hypothetical state the gas would assume if it obeyed the ideal gas equation at a pressure of 1 bar
  • For a gaseous or solid solute present in a diluted ideal solution: the hypothetical state of concentration of the solute of exactly one mole per liter (1 M) at a pressure of 1 bar extrapolated from infinite dilution
  • For a pure substance or a solvent in a condensed state (a liquid or a solid): the standard state is the pure liquid or solid under a pressure of 1 bar

For elements that have multiple allotropes, the reference state usually is chosen to be the form in which the element is most stable under 1 bar of pressure. One exception is phosphorus, for which the most stable form at 1 bar is black phosphorus, but white phosphorus is chosen as the standard reference state for zero enthalpy of formation.[2]

For example, the standard enthalpy of formation of carbon dioxide would be the enthalpy of the following reaction under the above conditions:

All elements are written in their standard states, and one mole of product is formed. This is true for all enthalpies of formation.

The standard enthalpy of formation is measured in units of energy per amount of substance, usually stated in kilojoule per mole (kJ mol−1), but also in kilocalorie per mole, joule per mole or kilocalorie per gram (any combination of these units conforming to the energy per mass or amount guideline).

All elements in their reference states (oxygen gas, solid carbon in the form of graphite, etc.) have a standard enthalpy of formation of zero, as there is no change involved in their formation.

The formation reaction is a constant pressure and constant temperature process. Since the pressure of the standard formation reaction is fixed at 1 bar, the standard formation enthalpy or reaction heat is a function of temperature. For tabulation purposes, standard formation enthalpies are all given at a single temperature: 298 K, represented by the symbol ΔfH
298 K
.

Hess's law

For many substances, the formation reaction may be considered as the sum of a number of simpler reactions, either real or fictitious. The enthalpy of reaction can then be analyzed by applying Hess's Law, which states that the sum of the enthalpy changes for a number of individual reaction steps equals the enthalpy change of the overall reaction. This is true because enthalpy is a state function, whose value for an overall process depends only on the initial and final states and not on any intermediate states. Examples are given in the following sections.

Ionic compounds: Born–Haber cycle

 
Standard enthalpy change of formation in Born–Haber diagram for lithium fluoride. ΔHlatt corresponds to UL in the text. The downward arrow "electron affinity" shows the negative quantity –EAF, since EAF is usually defined as positive.

For ionic compounds, the standard enthalpy of formation is equivalent to the sum of several terms included in the Born–Haber cycle. For example, the formation of lithium fluoride,

 

may be considered as the sum of several steps, each with its own enthalpy (or energy, approximately):

  1. Hsub, the standard enthalpy of atomization (or sublimation) of solid lithium.
  2. IELi, the first ionization energy of gaseous lithium.
  3. B(F–F), the standard enthalpy of atomization (or bond energy) of fluorine gas.
  4. EAF, the electron affinity of a fluorine atom.
  5. UL, the lattice energy of lithium fluoride.

The sum of all these enthalpies will give the standard enthalpy of formation (ΔHf) of lithium fluoride:

 

In practice, the enthalpy of formation of lithium fluoride can be determined experimentally, but the lattice energy cannot be measured directly. The equation is therefore rearranged in order to evaluate the lattice energy:[3]

 

Organic compounds

The formation reactions for most organic compounds are hypothetical. For instance, carbon and hydrogen won't directly react to form methane (CH4), so that the standard enthalpy of formation cannot be measured directly. However the standard enthalpy of combustion is readily measurable using bomb calorimetry. The standard enthalpy of formation is then determined using Hess's law. The combustion of methane:

 

is equivalent to the sum of the hypothetical decomposition into elements followed by the combustion of the elements to form carbon dioxide (CO2) and water (H2O):

 
 
 

Applying Hess's law,

 

Solving for the standard of enthalpy of formation,

 

The value of   is determined to be −74.8 kJ/mol. The negative sign shows that the reaction, if it were to proceed, would be exothermic; that is, methane is enthalpically more stable than hydrogen gas and carbon.

It is possible to predict heats of formation for simple unstrained organic compounds with the heat of formation group additivity method.

Use in calculation for other reactions

The standard enthalpy change of any reaction can be calculated from the standard enthalpies of formation of reactants and products using Hess's law. A given reaction is considered as the decomposition of all reactants into elements in their standard states, followed by the formation of all products. The heat of reaction is then minus the sum of the standard enthalpies of formation of the reactants (each being multiplied by its respective stoichiometric coefficient, ν) plus the sum of the standard enthalpies of formation of the products (each also multiplied by its respective stoichiometric coefficient), as shown in the equation below:[4]

 

If the standard enthalpy of the products is less than the standard enthalpy of the reactants, the standard enthalpy of reaction is negative. This implies that the reaction is exothermic. The converse is also true; the standard enthalpy of reaction is positive for an endothermic reaction. This calculation has a tacit assumption of ideal solution between reactants and products where the enthalpy of mixing is zero.

For example, for the combustion of methane,  :

 

However   is an element in its standard state, so that  , and the heat of reaction is simplified to

 

which is the equation in the previous section for the enthalpy of combustion  .

Key concepts for enthalpy calculations

  • When a reaction is reversed, the magnitude of ΔH stays the same, but the sign changes.
  • When the balanced equation for a reaction is multiplied by an integer, the corresponding value of ΔH must be multiplied by that integer as well.
  • The change in enthalpy for a reaction can be calculated from the enthalpies of formation of the reactants and the products
  • Elements in their standard states make no contribution to the enthalpy calculations for the reaction, since the enthalpy of an element in its standard state is zero. Allotropes of an element other than the standard state generally have non-zero standard enthalpies of formation.

Examples: standard enthalpies of formation at 25 °C

Thermochemical properties of selected substances at 298.15 K and 1 atm

Inorganic substances

Species Phase Chemical formula ΔfH /(kJ/mol)
Aluminium
Aluminium Solid Al 0
Aluminium chloride Solid AlCl3 −705.63
Aluminium oxide Solid Al2O3 −1675.5
Aluminium hydroxide Solid Al(OH)3 −1277
Aluminium sulphate Solid Al2(SO4)3 −3440
Barium
Barium chloride Solid BaCl2 −858.6
Barium carbonate Solid BaCO3 −1216
Barium hydroxide Solid Ba(OH)2 −944.7
Barium oxide Solid BaO −548.1
Barium sulfate Solid BaSO4 −1473.3
Beryllium
Beryllium Solid Be 0
Beryllium hydroxide Solid Be(OH)2 −903
Beryllium oxide Solid BeO −609.4
Boron
Boron trichloride Solid BCl3 −402.96
Bromine
Bromine Liquid Br2 0
Bromide ion Aqueous Br −121
Bromine Gas Br 111.884
Bromine Gas Br2 30.91
Bromine trifluoride Gas BrF3 −255.60
Hydrogen bromide Gas HBr −36.29
Cadmium
Cadmium Solid Cd 0
Cadmium oxide Solid CdO −258
Cadmium hydroxide Solid Cd(OH)2 −561
Cadmium sulfide Solid CdS −162
Cadmium sulfate Solid CdSO4 −935
Caesium
Caesium Solid Cs 0
Caesium Gas Cs 76.50
Caesium Liquid Cs 2.09
Caesium(I) ion Gas Cs+ 457.964
Caesium chloride Solid CsCl −443.04
Calcium
Calcium Solid Ca 0
Calcium Gas Ca 178.2
Calcium(II) ion Gas Ca2+ 1925.90
Calcium(II) ion Aqueous Ca2+ −542.7
Calcium carbide Solid CaC2 −59.8
Calcium carbonate (Calcite) Solid CaCO3 −1206.9
Calcium chloride Solid CaCl2 −795.8
Calcium chloride Aqueous CaCl2 −877.3
Calcium phosphate Solid Ca3(PO4)2 −4132
Calcium fluoride Solid CaF2 −1219.6
Calcium hydride Solid CaH2 −186.2
Calcium hydroxide Solid Ca(OH)2 −986.09
Calcium hydroxide Aqueous Ca(OH)2 −1002.82
Calcium oxide Solid CaO −635.09
Calcium sulfate Solid CaSO4 −1434.52
Calcium sulfide Solid CaS −482.4
Wollastonite Solid CaSiO3 −1630
Carbon
Carbon (Graphite) Solid C 0
Carbon (Diamond) Solid C 1.9
Carbon Gas C 716.67
Carbon dioxide Gas CO2 −393.509
Carbon disulfide Liquid CS2 89.41
Carbon disulfide Gas CS2 116.7
Carbon monoxide Gas CO −110.525
Carbonyl chloride (Phosgene) Gas COCl2 −218.8
Carbon dioxide (un–ionized) Aqueous CO2(aq) −419.26
Bicarbonate ion Aqueous HCO3 −689.93
Carbonate ion Aqueous CO32– −675.23
Chlorine
Monatomic chlorine Gas Cl 121.7
Chloride ion Aqueous Cl −167.2
Chlorine Gas Cl2 0
Chromium
Chromium Solid Cr 0
Copper
Copper Solid Cu 0
Copper(II) oxide Solid CuO −155.2
Copper(II) sulfate Aqueous CuSO4 −769.98
Fluorine
Fluorine Gas F2 0
Hydrogen
Monatomic hydrogen Gas H 218
Hydrogen Gas H2 0
Water Gas H2O −241.818
Water Liquid H2O −285.8
Hydrogen ion Aqueous H+ 0
Hydroxide ion Aqueous OH −230
Hydrogen peroxide Liquid H2O2 −187.8
Phosphoric acid Liquid H3PO4 −1288
Hydrogen cyanide Gas HCN 130.5
Hydrogen bromide Liquid HBr −36.3
Hydrogen chloride Gas HCl −92.30
Hydrogen chloride Aqueous HCl −167.2
Hydrogen fluoride Gas HF −273.3
Hydrogen iodide Gas HI 26.5
Iodine
Iodine Solid I2 0
Iodine Gas I2 62.438
Iodine Aqueous I2 23
Iodide ion Aqueous I −55
Iron
Iron Solid Fe 0
Iron carbide (Cementite) Solid Fe3C 5.4
Iron(II) carbonate (Siderite) Solid FeCO3 −750.6
Iron(III) chloride Solid FeCl3 −399.4
Iron(II) oxide (Wüstite) Solid FeO −272
Iron(II,III) oxide (Magnetite) Solid Fe3O4 −1118.4
Iron(III) oxide (Hematite) Solid Fe2O3 −824.2
Iron(II) sulfate Solid FeSO4 −929
Iron(III) sulfate Solid Fe2(SO4)3 −2583
Iron(II) sulfide Solid FeS −102
Pyrite Solid FeS2 −178
Lead
Lead Solid Pb 0
Lead dioxide Solid PbO2 −277
Lead sulfide Solid PbS −100
Lead sulfate Solid PbSO4 −920
Lead(II) nitrate Solid Pb(NO3)2 −452
Lead(II) sulfate Solid PbSO4 −920
Lithium
Lithium fluoride Solid LiF −616.93
Magnesium
Magnesium Solid Mg 0
Magnesium ion Aqueous Mg2+ −466.85
Magnesium carbonate Solid MgCO3 −1095.797
Magnesium chloride Solid MgCl2 −641.8
Magnesium hydroxide Solid Mg(OH)2 −924.54
Magnesium hydroxide Aqueous Mg(OH)2 −926.8
Magnesium oxide Solid MgO −601.6
Magnesium sulfate Solid MgSO4 −1278.2
Manganese
Manganese Solid Mn 0
Manganese(II) oxide Solid MnO −384.9
Manganese(IV) oxide Solid MnO2 −519.7
Manganese(III) oxide Solid Mn2O3 −971
Manganese(II,III) oxide Solid Mn3O4 −1387
Permanganate Aqueous MnO
4
−543
Mercury
Mercury(II) oxide (red) Solid HgO −90.83
Mercury sulfide (red, cinnabar) Solid HgS −58.2
Nitrogen
Nitrogen Gas N2 0
Ammonia (ammonium hydroxide) Aqueous NH3 (NH4OH) −80.8
Ammonia Gas NH3 −46.1
Ammonium nitrate Solid NH4NO3 −365.6
Ammonium chloride Solid NH4Cl −314.55
Nitrogen dioxide Gas NO2 33.2
Hydrazine Gas N2H4 95.4
Hydrazine Liquid N2H4 50.6
Nitrous oxide Gas N2O 82.05
Nitric oxide Gas NO 90.29
Dinitrogen tetroxide Gas N2O4 9.16
Dinitrogen pentoxide Solid N2O5 −43.1
Dinitrogen pentoxide Gas N2O5 11.3
Nitric acid Aqueous HNO3 −207
Oxygen
Monatomic oxygen Gas O 249
Oxygen Gas O2 0
Ozone Gas O3 143
Phosphorus
White phosphorus Solid P4 0
Red phosphorus Solid P −17.4[5]
Black phosphorus Solid P −39.3[5]
Phosphorus trichloride Liquid PCl3 −319.7
Phosphorus trichloride Gas PCl3 −278
Phosphorus pentachloride Solid PCl5 −440
Phosphorus pentachloride Gas PCl5 −321
Phosphorus pentoxide Solid P2O5 −1505.5[6]
Potassium
Potassium bromide Solid KBr −392.2
Potassium carbonate Solid K2CO3 −1150
Potassium chlorate Solid KClO3 −391.4
Potassium chloride Solid KCl −436.68
Potassium fluoride Solid KF −562.6
Potassium oxide Solid K2O −363
Potassium nitrate Solid KNO3 −494.5
Potassium perchlorate Solid KClO4 −430.12
Silicon
Silicon Gas Si 368.2
Silicon carbide Solid SiC −74.4,[7] −71.5[8]
Silicon tetrachloride Liquid SiCl4 −640.1
Silica (Quartz) Solid SiO2 −910.86
Silver
Silver bromide Solid AgBr −99.5
Silver chloride Solid AgCl −127.01
Silver iodide Solid AgI −62.4
Silver oxide Solid Ag2O −31.1
Silver sulfide Solid Ag2S −31.8
Sodium
Sodium Solid Na 0
Sodium Gas Na 107.5
Sodium bicarbonate Solid NaHCO3 −950.8
Sodium carbonate Solid Na2CO3 −1130.77
Sodium chloride Aqueous NaCl −407.27
Sodium chloride Solid NaCl −411.12
Sodium chloride Liquid NaCl −385.92
Sodium chloride Gas NaCl −181.42
Sodium chlorate Solid NaClO3 −365.4
Sodium fluoride Solid NaF −569.0
Sodium hydroxide Aqueous NaOH −469.15
Sodium hydroxide Solid NaOH −425.93
Sodium hypochlorite Solid NaOCl −347.1
Sodium nitrate Aqueous NaNO3 −446.2
Sodium nitrate Solid NaNO3 −424.8
Sodium oxide Solid Na2O −414.2
Sulfur
Sulfur (monoclinic) Solid S8 0.3
Sulfur (rhombic) Solid S8 0
Hydrogen sulfide Gas H2S −20.63
Sulfur dioxide Gas SO2 −296.84
Sulfur trioxide Gas SO3 −395.7
Sulfuric acid Liquid H2SO4 −814
Tin
Titanium
Titanium Gas Ti 468
Titanium tetrachloride Gas TiCl4 −763.2
Titanium tetrachloride Liquid TiCl4 −804.2
Titanium dioxide Solid TiO2 −944.7
Zinc
Zinc Gas Zn 130.7
Zinc chloride Solid ZnCl2 −415.1
Zinc oxide Solid ZnO −348.0
Zinc sulfate Solid ZnSO4 −980.14

Aliphatic hydrocarbons

Formula Name ΔfH /(kcal/mol) ΔfH /(kJ/mol)
Straight-chain
CH4 Methane −17.9 −74.9
C2H6 Ethane −20.0 −83.7
C2H4 Ethylene 12.5 52.5
C2H2 Acetylene 54.2 226.8
C3H8 Propane −25.0 −104.6
C4H10 n-Butane −30.0 −125.5
C5H12 n-Pentane −35.1 −146.9
C6H14 n-Hexane −40.0 −167.4
C7H16 n-Heptane −44.9 −187.9
C8H18 n-Octane −49.8 −208.4
C9H20 n-Nonane −54.8 −229.3
C10H22 n-Decane −59.6 −249.4
C4 Alkane branched isomers
C4H10 Isobutane (methylpropane) −32.1 −134.3
C5 Alkane branched isomers
C5H12 Neopentane (dimethylpropane) −40.1 −167.8
C5H12 Isopentane (methylbutane) −36.9 −154.4
C6 Alkane branched isomers
C6H14 2,2-Dimethylbutane −44.5 −186.2
C6H14 2,3-Dimethylbutane −42.5 −177.8
C6H14 2-Methylpentane (isohexane) −41.8 −174.9
C6H14 3-Methylpentane −41.1 −172.0
C7 Alkane branched isomers
C7H16 2,2-Dimethylpentane −49.2 −205.9
C7H16 2,2,3-Trimethylbutane −49.0 −205.0
C7H16 3,3-Dimethylpentane −48.1 −201.3
C7H16 2,3-Dimethylpentane −47.3 −197.9
C7H16 2,4-Dimethylpentane −48.2 −201.7
C7H16 2-Methylhexane −46.5 −194.6
C7H16 3-Methylhexane −45.7 −191.2
C7H16 3-Ethylpentane −45.3 −189.5
C8 Alkane branched isomers
C8H18 2,3-Dimethylhexane −55.1 −230.5
C8H18 2,2,3,3-Tetramethylbutane −53.9 −225.5
C8H18 2,2-Dimethylhexane −53.7 −224.7
C8H18 2,2,4-Trimethylpentane (isooctane) −53.5 −223.8
C8H18 2,5-Dimethylhexane −53.2 −222.6
C8H18 2,2,3-Trimethylpentane −52.6 −220.1
C8H18 3,3-Dimethylhexane −52.6 −220.1
C8H18 2,4-Dimethylhexane −52.4 −219.2
C8H18 2,3,4-Trimethylpentane −51.9 −217.1
C8H18 2,3,3-Trimethylpentane −51.7 −216.3
C8H18 2-Methylheptane −51.5 −215.5
C8H18 3-Ethyl-3-Methylpentane −51.4 −215.1
C8H18 3,4-Dimethylhexane −50.9 −213.0
C8H18 3-Ethyl-2-Methylpentane −50.4 −210.9
C8H18 3-Methylheptane −60.3 −252.5
C8H18 4-Methylheptane ? ?
C8H18 3-Ethylhexane ? ?
C9 Alkane branched isomers (selected)
C9H20 2,2,4,4-Tetramethylpentane −57.8 −241.8
C9H20 2,2,3,3-Tetramethylpentane −56.7 −237.2
C9H20 2,2,3,4-Tetramethylpentane −56.6 −236.8
C9H20 2,3,3,4-Tetramethylpentane −56.4 −236.0
C9H20 3,3-Diethylpentane −55.7 −233.0

Other organic compounds

Species Phase Chemical formula ΔfH /(kJ/mol)
Acetone Liquid C3H6O −248.4
Benzene Liquid C6H6 48.95
Benzoic acid Solid C7H6O2 −385.2
Carbon tetrachloride Liquid CCl4 −135.4
Carbon tetrachloride Gas CCl4 −95.98
Ethanol Liquid C2H5OH −277.0
Ethanol Gas C2H5OH −235.3
Glucose Solid C6H12O6 −1271
Isopropanol Gas C3H7OH −318.1
Methanol (methyl alcohol) Liquid CH3OH −238.4
Methanol (methyl alcohol) Gas CH3OH −201.0
Methyl linoleate (Biodiesel) Gas C19H34O2 −356.3
Sucrose Solid C12H22O11 −2226.1
Trichloromethane (Chloroform) Liquid CHCl3 −134.47
Trichloromethane (Chloroform) Gas CHCl3 −103.18
Vinyl chloride Solid C2H3Cl −94.12

See also

References

  1. ^ IUPAC, Compendium of Chemical Terminology, 2nd ed. (the "Gold Book") (1997). Online corrected version: (2006–) "standard pressure". doi:10.1351/goldbook.S05921
  2. ^ Oxtoby, David W; Pat Gillis, H; Campion, Alan (2011). Principles of Modern Chemistry. p. 547. ISBN 978-0-8400-4931-5.
  3. ^ Moore, Stanitski, and Jurs. Chemistry: The Molecular Science. 3rd edition. 2008. ISBN 0-495-10521-X. pages 320–321.
  4. ^ "Enthalpies of Reaction". www.science.uwaterloo.ca. from the original on 25 October 2017. Retrieved 2 May 2018.
  5. ^ a b Housecroft, C. E.; Sharpe, A. G. (2004). Inorganic Chemistry (2nd ed.). Prentice Hall. p. 392. ISBN 978-0-13-039913-7.
  6. ^ Green, D.W., ed. (2007). Perry's Chemical Engineers' Handbook (8th ed.). Mcgraw-Hill. p. 2–191. ISBN 9780071422949.
  7. ^ Kleykamp, H. (1998). "Gibbs Energy of Formation of SiC: A contribution to the Thermodynamic Stability of the Modifications". Berichte der Bunsengesellschaft für physikalische Chemie. 102 (9): 1231–1234. doi:10.1002/bbpc.19981020928.
  8. ^ "Silicon Carbide, Alpha (SiC)". March 1967. Retrieved 5 February 2019.
  • Zumdahl, Steven (2009). Chemical Principles (6th ed.). Boston. New York: Houghton Mifflin. pp. 384–387. ISBN 978-0-547-19626-8.

External links

  • NIST Chemistry WebBook

standard, enthalpy, formation, chemistry, thermodynamics, standard, enthalpy, formation, standard, heat, formation, compound, change, enthalpy, during, formation, mole, substance, from, constituent, elements, their, reference, state, with, substances, their, s. In chemistry and thermodynamics the standard enthalpy of formation or standard heat of formation of a compound is the change of enthalpy during the formation of 1 mole of the substance from its constituent elements in their reference state with all substances in their standard states The standard pressure value p 105 Pa 100 kPa 1 bar is recommended by IUPAC although prior to 1982 the value 1 00 atm 101 325 kPa was used 1 There is no standard temperature Its symbol is DfH The superscript Plimsoll on this symbol indicates that the process has occurred under standard conditions at the specified temperature usually 25 C or 298 15 K Standard states are as follows For a gas the hypothetical state the gas would assume if it obeyed the ideal gas equation at a pressure of 1 bar For a gaseous or solid solute present in a diluted ideal solution the hypothetical state of concentration of the solute of exactly one mole per liter 1 M at a pressure of 1 bar extrapolated from infinite dilution For a pure substance or a solvent in a condensed state a liquid or a solid the standard state is the pure liquid or solid under a pressure of 1 barFor elements that have multiple allotropes the reference state usually is chosen to be the form in which the element is most stable under 1 bar of pressure One exception is phosphorus for which the most stable form at 1 bar is black phosphorus but white phosphorus is chosen as the standard reference state for zero enthalpy of formation 2 For example the standard enthalpy of formation of carbon dioxide would be the enthalpy of the following reaction under the above conditions C s graphite O 2 g CO 2 g displaystyle ce C s graphite O2 g gt CO2 g All elements are written in their standard states and one mole of product is formed This is true for all enthalpies of formation The standard enthalpy of formation is measured in units of energy per amount of substance usually stated in kilojoule per mole kJ mol 1 but also in kilocalorie per mole joule per mole or kilocalorie per gram any combination of these units conforming to the energy per mass or amount guideline All elements in their reference states oxygen gas solid carbon in the form of graphite etc have a standard enthalpy of formation of zero as there is no change involved in their formation The formation reaction is a constant pressure and constant temperature process Since the pressure of the standard formation reaction is fixed at 1 bar the standard formation enthalpy or reaction heat is a function of temperature For tabulation purposes standard formation enthalpies are all given at a single temperature 298 K represented by the symbol DfH 298 K Contents 1 Hess s law 2 Ionic compounds Born Haber cycle 3 Organic compounds 4 Use in calculation for other reactions 5 Key concepts for enthalpy calculations 6 Examples standard enthalpies of formation at 25 C 6 1 Inorganic substances 6 2 Aliphatic hydrocarbons 6 3 Other organic compounds 7 See also 8 References 9 External linksHess s law EditFor many substances the formation reaction may be considered as the sum of a number of simpler reactions either real or fictitious The enthalpy of reaction can then be analyzed by applying Hess s Law which states that the sum of the enthalpy changes for a number of individual reaction steps equals the enthalpy change of the overall reaction This is true because enthalpy is a state function whose value for an overall process depends only on the initial and final states and not on any intermediate states Examples are given in the following sections Ionic compounds Born Haber cycle Edit Standard enthalpy change of formation in Born Haber diagram for lithium fluoride DHlatt corresponds to UL in the text The downward arrow electron affinity shows the negative quantity EAF since EAF is usually defined as positive For ionic compounds the standard enthalpy of formation is equivalent to the sum of several terms included in the Born Haber cycle For example the formation of lithium fluoride Li s 1 2 F 2 g LiF s displaystyle ce Li s 1 2F2 g gt LiF s may be considered as the sum of several steps each with its own enthalpy or energy approximately Hsub the standard enthalpy of atomization or sublimation of solid lithium IELi the first ionization energy of gaseous lithium B F F the standard enthalpy of atomization or bond energy of fluorine gas EAF the electron affinity of a fluorine atom UL the lattice energy of lithium fluoride The sum of all these enthalpies will give the standard enthalpy of formation DHf of lithium fluoride D H f D H sub IE Li 1 2 B F F EA F U L displaystyle Delta H text f Delta H text sub text IE text Li frac 1 2 text B F F text EA text F text U text L In practice the enthalpy of formation of lithium fluoride can be determined experimentally but the lattice energy cannot be measured directly The equation is therefore rearranged in order to evaluate the lattice energy 3 U L D H sub IE Li 1 2 B F F EA F D H f displaystyle U text L Delta H text sub text IE text Li frac 1 2 text B F F text EA text F Delta H text f Organic compounds EditThe formation reactions for most organic compounds are hypothetical For instance carbon and hydrogen won t directly react to form methane CH4 so that the standard enthalpy of formation cannot be measured directly However the standard enthalpy of combustion is readily measurable using bomb calorimetry The standard enthalpy of formation is then determined using Hess s law The combustion of methane CH 4 2 O 2 CO 2 2 H 2 O displaystyle ce CH4 2 O2 gt CO2 2 H2O is equivalent to the sum of the hypothetical decomposition into elements followed by the combustion of the elements to form carbon dioxide CO2 and water H2O CH 4 C 2 H 2 displaystyle ce CH4 gt C 2H2 C O 2 CO 2 displaystyle ce C O2 gt CO2 2 H 2 O 2 2 H 2 O displaystyle ce 2H2 O2 gt 2H2O Applying Hess s law D comb H CH 4 D f H CO 2 2 D f H H 2 O D f H CH 4 displaystyle Delta text comb H ominus text CH 4 Delta text f H ominus text CO 2 2 Delta text f H ominus text H 2 text O Delta text f H ominus text CH 4 Solving for the standard of enthalpy of formation D f H CH 4 D f H CO 2 2 D f H H 2 O D comb H CH 4 displaystyle Delta text f H ominus text CH 4 Delta text f H ominus text CO 2 2 Delta text f H ominus text H 2 text O Delta text comb H ominus text CH 4 The value of D f H CH 4 displaystyle Delta text f H ominus text CH 4 is determined to be 74 8 kJ mol The negative sign shows that the reaction if it were to proceed would be exothermic that is methane is enthalpically more stable than hydrogen gas and carbon It is possible to predict heats of formation for simple unstrained organic compounds with the heat of formation group additivity method Use in calculation for other reactions EditThe standard enthalpy change of any reaction can be calculated from the standard enthalpies of formation of reactants and products using Hess s law A given reaction is considered as the decomposition of all reactants into elements in their standard states followed by the formation of all products The heat of reaction is then minus the sum of the standard enthalpies of formation of the reactants each being multiplied by its respective stoichiometric coefficient n plus the sum of the standard enthalpies of formation of the products each also multiplied by its respective stoichiometric coefficient as shown in the equation below 4 D r H n D f H products n D f H reactants displaystyle Delta text r H ominus sum nu Delta text f H ominus text products sum nu Delta text f H ominus text reactants If the standard enthalpy of the products is less than the standard enthalpy of the reactants the standard enthalpy of reaction is negative This implies that the reaction is exothermic The converse is also true the standard enthalpy of reaction is positive for an endothermic reaction This calculation has a tacit assumption of ideal solution between reactants and products where the enthalpy of mixing is zero For example for the combustion of methane CH 4 2 O 2 CO 2 2 H 2 O displaystyle ce CH4 2O2 gt CO2 2H2O D r H D f H CO 2 2 D f H H 2 O D f H CH 4 2 D f H O 2 displaystyle Delta text r H ominus Delta text f H ominus text CO 2 2 Delta text f H ominus text H 2 text O Delta text f H ominus text CH 4 2 Delta text f H ominus text O 2 However O 2 displaystyle ce O2 is an element in its standard state so that D f H O 2 0 displaystyle Delta text f H ominus text O 2 0 and the heat of reaction is simplified to D r H D f H CO 2 2 D f H H 2 O D f H CH 4 displaystyle Delta text r H ominus Delta text f H ominus text CO 2 2 Delta text f H ominus text H 2 text O Delta text f H ominus text CH 4 which is the equation in the previous section for the enthalpy of combustion D comb H displaystyle Delta text comb H ominus Key concepts for enthalpy calculations EditWhen a reaction is reversed the magnitude of DH stays the same but the sign changes When the balanced equation for a reaction is multiplied by an integer the corresponding value of DH must be multiplied by that integer as well The change in enthalpy for a reaction can be calculated from the enthalpies of formation of the reactants and the products Elements in their standard states make no contribution to the enthalpy calculations for the reaction since the enthalpy of an element in its standard state is zero Allotropes of an element other than the standard state generally have non zero standard enthalpies of formation Examples standard enthalpies of formation at 25 C EditThermochemical properties of selected substances at 298 15 K and 1 atm Inorganic substances Edit Species Phase Chemical formula DfH kJ mol AluminiumAluminium Solid Al 0Aluminium chloride Solid AlCl3 705 63Aluminium oxide Solid Al2O3 1675 5Aluminium hydroxide Solid Al OH 3 1277Aluminium sulphate Solid Al2 SO4 3 3440BariumBarium chloride Solid BaCl2 858 6Barium carbonate Solid BaCO3 1216Barium hydroxide Solid Ba OH 2 944 7Barium oxide Solid BaO 548 1Barium sulfate Solid BaSO4 1473 3BerylliumBeryllium Solid Be 0Beryllium hydroxide Solid Be OH 2 903Beryllium oxide Solid BeO 609 4BoronBoron trichloride Solid BCl3 402 96BromineBromine Liquid Br2 0Bromide ion Aqueous Br 121Bromine Gas Br 111 884Bromine Gas Br2 30 91Bromine trifluoride Gas BrF3 255 60Hydrogen bromide Gas HBr 36 29CadmiumCadmium Solid Cd 0Cadmium oxide Solid CdO 258Cadmium hydroxide Solid Cd OH 2 561Cadmium sulfide Solid CdS 162Cadmium sulfate Solid CdSO4 935CaesiumCaesium Solid Cs 0Caesium Gas Cs 76 50Caesium Liquid Cs 2 09Caesium I ion Gas Cs 457 964Caesium chloride Solid CsCl 443 04CalciumCalcium Solid Ca 0Calcium Gas Ca 178 2Calcium II ion Gas Ca2 1925 90Calcium II ion Aqueous Ca2 542 7Calcium carbide Solid CaC2 59 8Calcium carbonate Calcite Solid CaCO3 1206 9Calcium chloride Solid CaCl2 795 8Calcium chloride Aqueous CaCl2 877 3Calcium phosphate Solid Ca3 PO4 2 4132Calcium fluoride Solid CaF2 1219 6Calcium hydride Solid CaH2 186 2Calcium hydroxide Solid Ca OH 2 986 09Calcium hydroxide Aqueous Ca OH 2 1002 82Calcium oxide Solid CaO 635 09Calcium sulfate Solid CaSO4 1434 52Calcium sulfide Solid CaS 482 4Wollastonite Solid CaSiO3 1630CarbonCarbon Graphite Solid C 0Carbon Diamond Solid C 1 9Carbon Gas C 716 67Carbon dioxide Gas CO2 393 509Carbon disulfide Liquid CS2 89 41Carbon disulfide Gas CS2 116 7Carbon monoxide Gas CO 110 525Carbonyl chloride Phosgene Gas COCl2 218 8Carbon dioxide un ionized Aqueous CO2 aq 419 26Bicarbonate ion Aqueous HCO3 689 93Carbonate ion Aqueous CO32 675 23ChlorineMonatomic chlorine Gas Cl 121 7Chloride ion Aqueous Cl 167 2Chlorine Gas Cl2 0ChromiumChromium Solid Cr 0CopperCopper Solid Cu 0Copper II oxide Solid CuO 155 2Copper II sulfate Aqueous CuSO4 769 98FluorineFluorine Gas F2 0HydrogenMonatomic hydrogen Gas H 218Hydrogen Gas H2 0Water Gas H2O 241 818Water Liquid H2O 285 8Hydrogen ion Aqueous H 0Hydroxide ion Aqueous OH 230Hydrogen peroxide Liquid H2O2 187 8Phosphoric acid Liquid H3PO4 1288Hydrogen cyanide Gas HCN 130 5Hydrogen bromide Liquid HBr 36 3Hydrogen chloride Gas HCl 92 30Hydrogen chloride Aqueous HCl 167 2Hydrogen fluoride Gas HF 273 3Hydrogen iodide Gas HI 26 5IodineIodine Solid I2 0Iodine Gas I2 62 438Iodine Aqueous I2 23Iodide ion Aqueous I 55IronIron Solid Fe 0Iron carbide Cementite Solid Fe3C 5 4Iron II carbonate Siderite Solid FeCO3 750 6Iron III chloride Solid FeCl3 399 4Iron II oxide Wustite Solid FeO 272Iron II III oxide Magnetite Solid Fe3O4 1118 4Iron III oxide Hematite Solid Fe2O3 824 2Iron II sulfate Solid FeSO4 929Iron III sulfate Solid Fe2 SO4 3 2583Iron II sulfide Solid FeS 102Pyrite Solid FeS2 178LeadLead Solid Pb 0Lead dioxide Solid PbO2 277Lead sulfide Solid PbS 100Lead sulfate Solid PbSO4 920Lead II nitrate Solid Pb NO3 2 452Lead II sulfate Solid PbSO4 920LithiumLithium fluoride Solid LiF 616 93MagnesiumMagnesium Solid Mg 0Magnesium ion Aqueous Mg2 466 85Magnesium carbonate Solid MgCO3 1095 797Magnesium chloride Solid MgCl2 641 8Magnesium hydroxide Solid Mg OH 2 924 54Magnesium hydroxide Aqueous Mg OH 2 926 8Magnesium oxide Solid MgO 601 6Magnesium sulfate Solid MgSO4 1278 2ManganeseManganese Solid Mn 0Manganese II oxide Solid MnO 384 9Manganese IV oxide Solid MnO2 519 7Manganese III oxide Solid Mn2O3 971Manganese II III oxide Solid Mn3O4 1387Permanganate Aqueous MnO 4 543MercuryMercury II oxide red Solid HgO 90 83Mercury sulfide red cinnabar Solid HgS 58 2NitrogenNitrogen Gas N2 0Ammonia ammonium hydroxide Aqueous NH3 NH4OH 80 8Ammonia Gas NH3 46 1Ammonium nitrate Solid NH4NO3 365 6Ammonium chloride Solid NH4Cl 314 55Nitrogen dioxide Gas NO2 33 2Hydrazine Gas N2H4 95 4Hydrazine Liquid N2H4 50 6Nitrous oxide Gas N2O 82 05Nitric oxide Gas NO 90 29Dinitrogen tetroxide Gas N2O4 9 16Dinitrogen pentoxide Solid N2O5 43 1Dinitrogen pentoxide Gas N2O5 11 3Nitric acid Aqueous HNO3 207OxygenMonatomic oxygen Gas O 249Oxygen Gas O2 0Ozone Gas O3 143PhosphorusWhite phosphorus Solid P4 0Red phosphorus Solid P 17 4 5 Black phosphorus Solid P 39 3 5 Phosphorus trichloride Liquid PCl3 319 7Phosphorus trichloride Gas PCl3 278Phosphorus pentachloride Solid PCl5 440Phosphorus pentachloride Gas PCl5 321Phosphorus pentoxide Solid P2O5 1505 5 6 PotassiumPotassium bromide Solid KBr 392 2Potassium carbonate Solid K2CO3 1150Potassium chlorate Solid KClO3 391 4Potassium chloride Solid KCl 436 68Potassium fluoride Solid KF 562 6Potassium oxide Solid K2O 363Potassium nitrate Solid KNO3 494 5Potassium perchlorate Solid KClO4 430 12SiliconSilicon Gas Si 368 2Silicon carbide Solid SiC 74 4 7 71 5 8 Silicon tetrachloride Liquid SiCl4 640 1Silica Quartz Solid SiO2 910 86SilverSilver bromide Solid AgBr 99 5Silver chloride Solid AgCl 127 01Silver iodide Solid AgI 62 4Silver oxide Solid Ag2O 31 1Silver sulfide Solid Ag2S 31 8SodiumSodium Solid Na 0Sodium Gas Na 107 5Sodium bicarbonate Solid NaHCO3 950 8Sodium carbonate Solid Na2CO3 1130 77Sodium chloride Aqueous NaCl 407 27Sodium chloride Solid NaCl 411 12Sodium chloride Liquid NaCl 385 92Sodium chloride Gas NaCl 181 42Sodium chlorate Solid NaClO3 365 4Sodium fluoride Solid NaF 569 0Sodium hydroxide Aqueous NaOH 469 15Sodium hydroxide Solid NaOH 425 93Sodium hypochlorite Solid NaOCl 347 1Sodium nitrate Aqueous NaNO3 446 2Sodium nitrate Solid NaNO3 424 8Sodium oxide Solid Na2O 414 2SulfurSulfur monoclinic Solid S8 0 3Sulfur rhombic Solid S8 0Hydrogen sulfide Gas H2S 20 63Sulfur dioxide Gas SO2 296 84Sulfur trioxide Gas SO3 395 7Sulfuric acid Liquid H2SO4 814TinTitaniumTitanium Gas Ti 468Titanium tetrachloride Gas TiCl4 763 2Titanium tetrachloride Liquid TiCl4 804 2Titanium dioxide Solid TiO2 944 7ZincZinc Gas Zn 130 7Zinc chloride Solid ZnCl2 415 1Zinc oxide Solid ZnO 348 0Zinc sulfate Solid ZnSO4 980 14Aliphatic hydrocarbons Edit Formula Name DfH kcal mol DfH kJ mol Straight chainCH4 Methane 17 9 74 9C2H6 Ethane 20 0 83 7C2H4 Ethylene 12 5 52 5C2H2 Acetylene 54 2 226 8C3H8 Propane 25 0 104 6C4H10 n Butane 30 0 125 5C5H12 n Pentane 35 1 146 9C6H14 n Hexane 40 0 167 4C7H16 n Heptane 44 9 187 9C8H18 n Octane 49 8 208 4C9H20 n Nonane 54 8 229 3C10H22 n Decane 59 6 249 4C4 Alkane branched isomersC4H10 Isobutane methylpropane 32 1 134 3C5 Alkane branched isomersC5H12 Neopentane dimethylpropane 40 1 167 8C5H12 Isopentane methylbutane 36 9 154 4C6 Alkane branched isomersC6H14 2 2 Dimethylbutane 44 5 186 2C6H14 2 3 Dimethylbutane 42 5 177 8C6H14 2 Methylpentane isohexane 41 8 174 9C6H14 3 Methylpentane 41 1 172 0C7 Alkane branched isomersC7H16 2 2 Dimethylpentane 49 2 205 9C7H16 2 2 3 Trimethylbutane 49 0 205 0C7H16 3 3 Dimethylpentane 48 1 201 3C7H16 2 3 Dimethylpentane 47 3 197 9C7H16 2 4 Dimethylpentane 48 2 201 7C7H16 2 Methylhexane 46 5 194 6C7H16 3 Methylhexane 45 7 191 2C7H16 3 Ethylpentane 45 3 189 5C8 Alkane branched isomersC8H18 2 3 Dimethylhexane 55 1 230 5C8H18 2 2 3 3 Tetramethylbutane 53 9 225 5C8H18 2 2 Dimethylhexane 53 7 224 7C8H18 2 2 4 Trimethylpentane isooctane 53 5 223 8C8H18 2 5 Dimethylhexane 53 2 222 6C8H18 2 2 3 Trimethylpentane 52 6 220 1C8H18 3 3 Dimethylhexane 52 6 220 1C8H18 2 4 Dimethylhexane 52 4 219 2C8H18 2 3 4 Trimethylpentane 51 9 217 1C8H18 2 3 3 Trimethylpentane 51 7 216 3C8H18 2 Methylheptane 51 5 215 5C8H18 3 Ethyl 3 Methylpentane 51 4 215 1C8H18 3 4 Dimethylhexane 50 9 213 0C8H18 3 Ethyl 2 Methylpentane 50 4 210 9C8H18 3 Methylheptane 60 3 252 5C8H18 4 Methylheptane C8H18 3 Ethylhexane C9 Alkane branched isomers selected C9H20 2 2 4 4 Tetramethylpentane 57 8 241 8C9H20 2 2 3 3 Tetramethylpentane 56 7 237 2C9H20 2 2 3 4 Tetramethylpentane 56 6 236 8C9H20 2 3 3 4 Tetramethylpentane 56 4 236 0C9H20 3 3 Diethylpentane 55 7 233 0Other organic compounds Edit Species Phase Chemical formula DfH kJ mol Acetone Liquid C3H6O 248 4Benzene Liquid C6H6 48 95Benzoic acid Solid C7H6O2 385 2Carbon tetrachloride Liquid CCl4 135 4Carbon tetrachloride Gas CCl4 95 98Ethanol Liquid C2H5OH 277 0Ethanol Gas C2H5OH 235 3Glucose Solid C6H12O6 1271Isopropanol Gas C3H7OH 318 1Methanol methyl alcohol Liquid CH3OH 238 4Methanol methyl alcohol Gas CH3OH 201 0Methyl linoleate Biodiesel Gas C19H34O2 356 3Sucrose Solid C12H22O11 2226 1Trichloromethane Chloroform Liquid CHCl3 134 47Trichloromethane Chloroform Gas CHCl3 103 18Vinyl chloride Solid C2H3Cl 94 12See also EditCalorimetry ThermochemistryReferences Edit IUPAC Compendium of Chemical Terminology 2nd ed the Gold Book 1997 Online corrected version 2006 standard pressure doi 10 1351 goldbook S05921 Oxtoby David W Pat Gillis H Campion Alan 2011 Principles of Modern Chemistry p 547 ISBN 978 0 8400 4931 5 Moore Stanitski and Jurs Chemistry The Molecular Science 3rd edition 2008 ISBN 0 495 10521 X pages 320 321 Enthalpies of Reaction www science uwaterloo ca Archived from the original on 25 October 2017 Retrieved 2 May 2018 a b Housecroft C E Sharpe A G 2004 Inorganic Chemistry 2nd ed Prentice Hall p 392 ISBN 978 0 13 039913 7 Green D W ed 2007 Perry s Chemical Engineers Handbook 8th ed Mcgraw Hill p 2 191 ISBN 9780071422949 Kleykamp H 1998 Gibbs Energy of Formation of SiC A contribution to the Thermodynamic Stability of the Modifications Berichte der Bunsengesellschaft fur physikalische Chemie 102 9 1231 1234 doi 10 1002 bbpc 19981020928 Silicon Carbide Alpha SiC March 1967 Retrieved 5 February 2019 Zumdahl Steven 2009 Chemical Principles 6th ed Boston New York Houghton Mifflin pp 384 387 ISBN 978 0 547 19626 8 External links EditNIST Chemistry WebBook Retrieved from https en wikipedia org w index php title Standard enthalpy of formation amp oldid 1145054542, wikipedia, wiki, book, books, library,

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